The invention relates to an electrospray ionization (ESI) device for forming a stream of ionized sample molecules. The device comprises a sample introduction zone for receiving a liquid-form sample, a tip for spraying the sample into aerosol or gaseous form, and a flow channel connecting the sample introduction zone and the tip. According to the invention, the flow channel comprises an array of transversely oriented microstructures adapted to passively transport the liquid-form sample introduced to the sample introduction zone to the tip by means of capillary forces. The invention concerns also a manufacturing method and applications of the ESI device, in particular mass spectrometry. The device can be used without external pumping of sample liquid.